Materials for electroluminescence and the utilization thereof

ABSTRACT

The present invention relates to organic semiconductors which contain structural units L=X and in addition structural units which emit light from the triplet state. The materials according to the invention are more soluble and easier to synthesise and are therefore more suitable for use in organic light-emitting diodes than comparative materials in accordance with the prior art.

CROSS REFERENCE TO RELATED PATENT APPLICATION

This application is a divisional of U.S. patent application Ser. No.10/576,920, filed Sep. 14, 2006, which is incorporated by reference inits entirety. U.S. patent application Ser. No. 10/576,920 is a nationalstage application (under 35 U.S.C. §371) of PCT/EP2004/011888, filedOct. 21, 2004 and claims the right of priority under 35 U.S.C. §119(a)-(d) German Patent Application No. DE 10 2004 003 008.1, filed Jan.20, 2004; and German Patent Application No. DE 103 49 033.7, filed Oct.22, 2003.

The present invention describes novel materials and material mixturesfor use in organic electronic components and the use thereof in displaysbased thereon.

For about 12 years, broadly based research has been under way on thecommercialisation of display and illumination elements based onpolymeric (organic) light-emitting diodes (PLEDs). This development wasinitiated by the fundamental developments disclosed in WO 90/13148. Afirst product in the form of a relatively small display (in a shaverfrom PHILIPS N.V.) has recently also been available on the market.However, significant improvements are still necessary in order to makethese displays a real competitor for the liquid-crystal displays (LCDs)which currently dominate the market or to surpass them.

A development which emerged a few years ago, especially in the area of“small molecule” displays, is the use of materials which are able toemit light from the triplet state and thus exhibit phosphorescenceinstead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999. 75,4-6). Theoretical considerations mean that an up to four-fold increasein energy and power efficiency is possible using triplet emitters ofthis type. However, whether this development will succeed is highlydependent on whether it is possible to find corresponding devicecompositions which are also able to implement these advantages in OLEDs.Essential conditions for practical applicability which may be mentionedhere are, in particular, efficient energy transfer to the tripletemitter (and consequently efficient light emission), a long operatinglifetime and a low use and operating voltage. In order to achieve this,the properties of the matrix material are also of crucial importance inaddition to the properties of the triplet emitter. While carbazolecompounds in particular were considered for this purpose for a long timeand showed initial good results, excellent results both with respect tothe efficiency and also to the lifetime of the devices have recentlybeen achieved with novel matrix materials based on keto and iminecompounds (unpublished application DE 10317556.3) or on phosphineoxides, sulfones and sulfoxides (unpublished application DE 10330761.3).

Efforts have increasingly been made recently to utilise theabove-mentioned advantages of vapour-depositable triplet emitters forpolymer applications too. Thus, so-called hybrid device structures arebeing considered which combine the advantages of small molecule OLEDswith those of polymer OLEDs (=PLEDs) and are formed by mixing thetriplet emitter into the polymer. On the other hand, the triplet emittercan also be covalently bonded to the polymer. Both methods have theadvantage that the compounds can be processed from solution and that anexpensive and complex vapour-deposition process as is necessary fordevices based on low-molecular-weight compounds is not necessary.Application from solution (for example with the aid of high-resolutionprinting processes) will have significant advantages in the long termover the vacuum evaporation process which is common today, in particularwith respect to scalability, structurability, coating efficiency andeconomy. Here too, a suitable matrix material is necessary which enablesefficient energy transfer to the triplet emitter and which, incombination therewith, has good lives with low operating voltages.

WO 04/070772 describes blends and copolymers of triplet emitters withcertain carbazole-containing conjugated polymers which result inefficient emission and reduced operating voltage. A further improvementhas been achieved by the introduction of certain bridged carbazoleunits, as described in the unpublished application DE 10328627.6.

In spite of the advances cited in the above-mentioned publications andapplications, however, there is still considerable potential forimprovement of corresponding materials in the area of triplet emitterswhich can be processed from solution. A significant need for improvementis furthermore regarded as being, inter alia, in the following fields:

-   (1) The efficiency of the electroluminescent elements must be    significantly increased further compared with the prior art in order    to bring them to the level of the devices obtained by vapour    deposition.-   (2) The lifetime of the electroluminescent elements should be    significantly increased compared with the prior art.-   (3) The solubility of the polymers and blends containing the bridged    carbazole units described above, which represent the closest prior    art, is still unsatisfactory. Thus, it is not possible, for example,    to copolymerise a high proportion of the bridged carbazole units    described therein, since this results in insoluble polymers.    However, soluble polymers are necessary for application.-   (4) Although the carbazole units described above already exhibit    quite good results in the application, a further disadvantage of    these units, apart from the restricted solubility, is, however, the    in some cases very complex chemical access to these compounds. It    would be desirable here to have available compounds and monomers    whose device properties are comparable or better, but which are    easier to synthesis.-   (5) The polymers and mixtures in accordance with the prior art    exhibit high oxygen sensitivity. Thus, they can only be processed    with careful exclusion of oxygen. Less sensitive substances would    clearly be of advantage here.

It is thus clear that there continues to be a great demand forimprovement here.

Surprisingly, it has been found that polymers and mixtures which containcertain structural units give, in combination with triplet emitters,significant improvements here compared with mixtures or polymers inaccordance with the prior art. These polymers and mixtures are readilyaccessible chemically by standard reactions or are in some cases evencommercially available and generally result in readily soluble polymers.In addition, they exhibit relatively low oxygen sensitivity, whichsignificantly simplifies their preparation and processing. They aretherefore a subject-matter of the present application.

WO 03/099901 contains a chance disclosure of a copolymer which is per sein accordance with the invention, comprising a polymer skeletoncontaining ester groups (or alternatively carbonyl, sulfone, sulfoxideor phosphine oxide groups) and copolymerised iridium and platinumcomplexes. The combination of polymer skeletons of this type withtriplet emitters are accordingly excluded from the invention.

U.S. Ser. No. 03/022,908 and U.S. Ser. No. 03/224,208 contain chancedisclosures of a blend, which is per se in accordance with theinvention, of a polymer containing covalently bonded triplet emittersand a charge-transport polymer, where two of the charge-transportpolymers mentioned (based on triarylamines) additionally carry keto orsulfone groups. Particular advantages of this combination are notmentioned. These blends are excluded from the invention.

The invention relates to organic semiconductors comprising

-   (A) at least one polymer,-   (B) at least one structural unit L=X, where the following applies to    the symbols used:    -   L is on each occurrence, identically or differently, (R¹)(R²)C,        (R¹)P, (R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P, (R¹)(R²)(R³)As,        (R¹)(R²)(R³)Sb, (R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se,        (R¹)(R²)Te, (R¹)(R²)S(═O), (R¹)(R²)Se(═O) or (R¹)(R²)Te(═O);    -   X is on each occurrence, identically or differently, O, S, Se or        N—R⁴, with the proviso that X is not S or Se if L stands for S,        Se or Te;    -   R¹, R², R³ is on each occurrence, identically or differently, H,        F, CN, N(R⁴)₂, a straight-chain, branched or cyclic alkyl,        alkoxy or thioalkoxy group having 1 to 40 C atoms, which may be        substituted by R⁵ or may also be unsubstituted, where one or        more non-adjacent CH₂ groups may be replaced by —R⁶C═CR⁶—,        —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶, —O—,        —S—, —NR⁶— or —CONR⁶— and where one or more H atoms may be        replaced by F, Cl, Br, I, CN or NO₂, or an aromatic or        heteroaromatic ring system having 1 to 40 C atoms, which may be        substituted by one or more radicals R⁵, where two or more        substituents R¹, R² and/or R³ may also with one another form a        mono- or polycyclic, aliphatic or aromatic ring system; all        substituents R¹ to R³ on one structural unit here must not be H        or F; the groups R¹ to R³ may furthermore optionally have bonds        to the polymer;    -   R⁴ is on each occurrence, identically or differently, a        straight-chain, branched or cyclic alkyl or alkoxy chain having        1 to 22 C atoms, in which, in addition, one or more non-adjacent        C atoms may be replaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂,        Sn(R⁶)₂, —NR⁶—, —O—, —S—, —CO—O—, —O—CO—O—, where, in addition,        one or more H atoms may be replaced by fluorine, an aryl,        heteroaryl or aryloxy group having 1 to 40 C atoms, which may        also be substituted by one or more radicals R⁶, or OH or N(R⁵)₂;    -   R⁵ is on each occurrence, identically or differently, R⁴ or CN,        B(R⁶)₂ or Si(R⁶)₃,    -   R⁶ is on each occurrence, identically or differently, H or an        aliphatic or aromatic hydrocarbon radical having 1 to 20 C        atoms; and-   (C) at least one triplet emitter;    with the proviso that mixtures of two polymers in which the first    polymer contains covalently bonded triplet emitters and the other is    a copolymer comprising tetraphenyldiaminobiphenyl units and diphenyl    sulfone ether or diphenyl ketone ether units are excluded; and    furthermore with the proviso that polymers containing on the one    hand covalently bonded triplet emitters and on the other hand units    of the formula (a) are excluded from the invention:

in which Ar¹ and Ar² each independently denote a tetravalent aromatichydrocarbon group or a tetravalent heterocyclic group;one of the units X¹ and X² denotes C(═O) or C(R¹)(R²) and the otherdenotes O, S, C(═O), S(═O), SO₂, Si(R³)(R⁴), N(R⁵), B(R⁶), P(R⁷) orP(═O)(R⁸); where the radicals R¹, R², R³, R⁴, R⁵, R⁷, and R⁸ in theformula (a) each independently denote a hydrogen atom, a halogen atom,an alkyl group, an alkoxy group, an alkylthio group, an alkylaminogroup, an aryl group, an aryloxy group, an arylthio group, an arylaminogroup, an arylalkyl group, an arylalkoxy group, an arylalkylthio group,an arylalkylamino group, an acyl group, an acyloxy group, an amidegroup, an imine group, a substituted silyl group, a substituted silyloxygroup, a substituted silylthio group, a substituted silylamino group, amonovalent heterocyclic group, an arylalkenyl group, an arylethynylgroup or a cyano group,M denotes a group which is represented by formula (b), formula (c) orformula (d)—Y¹—Y²—  formula (b)in which Y¹ and Y² each independently denote O, S, C(═O), S(═O), SO₂,C(R⁹)(R¹⁰), Si(R¹¹)(R¹²), N(R¹³), B(R¹⁴), P(R¹⁵) or P(═O)(R¹⁶),where the radicals R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ in theformula (b) each independently denote a hydrogen atom, a halogen atom,an alkyl group, an alkoxy group, an alkylthio group, an alkylaminogroup, an aryl group, an aryloxy group, an arylthio group, an arylaminogroup, an arylalkyl group, an arylalkoxy group, an arylalkylthio group,an arylalkylamino group, an acyl group, an acyloxy group, an amidegroup, an imine group, a substituted silyl group, a substituted silyloxygroup, a substituted silylthio group, a substituted silylamino group, amonovalent heterocyclic group, an arylalkenyl group, an arylethynylgroup or a cyano group,where Y¹ and Y² are not identical if Y¹ is not C(R⁹)(R¹⁰) orSi(R¹¹)(R¹²).]—Y³═Y⁴—  formula (c)in which Y³ and Y⁴ each independently denote N, B, P, C(R¹⁷) or Si(R¹⁸);the radicals R¹⁷ and R¹⁸ in the formula (c) each independently denote ahydrogen atom, a halogen atom, an alkyl group, an alkoxy group, analkylthio group, an alkylamino group, an aryl group, an aryloxy group,an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxygroup, an arylalkylthio group, an arylalkylamino group, an acyl group,an acyloxy group, an amide group, an imine group, a substituted silylgroup, a substituted silyloxy group, a substituted silylthio group, asubstituted silylamino group, a monovalent heterocyclic group, anarylalkenyl group, an arylethynyl group or a cyano group;—Y⁵—  formula (d)in which Y⁵ denotes O, S, C(═O), S(═O), SO₂, C(R¹⁹)(R²⁰), Si(R²¹)(R²²),N(R²³), B(R²⁴), P(R²⁵) or P(═O)(R²⁶);where the radicals R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵ and R²⁶ in theformula (d) each independently denote a hydrogen atom, a halogen atom,an alkyl group, an alkoxy group, an alkylthio group, an alkylaminogroup, an aryl group, an aryloxy group, an arylthio group, an arylaminogroup, an arylalkyl group, an arylalkoxy group, an arylalkylthio group,an arylalkylamino group, an acyl group, an acyloxy group, an amidegroup, an imine group, a substituted silyl group, a substituted silyloxygroup, a substituted silylthio group, a substituted silylamino group, amonovalent heterocyclic group, an arylalkenyl group, an arylethynylgroup or a cyano group;Z₁ denotes —CR³⁶═CR³⁷— or —C≡C—; R³⁶ and R³⁷ each independently denote ahydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclicgroup or a cyano group; d denotes 0 or 1.

The symbol “═” used above and below stands for a double bond in thesense of the Lewis notation.

Preferred structural units L=X, as described above, are thus selectedfrom the formulae (1) to (5)

where the symbols used have the following meaning:

-   X is on each occurrence, identically or differently, O, S, Se or-   N—R⁴, with the proviso that X cannot be S or Se for formulae (4) and    (5);-   Y is on each occurrence, identically or differently, P, As, Sb or    Bi;-   Z is on each occurrence, identically or differently, S, Se or Te;-   R¹ to R⁶ have the same meaning as described above.

The organic semiconductors according to the invention are preferably inthe form of amorphous compounds or amorphous mixtures.

For the purposes of this invention, an aromatic or heteroaromatic ringsystem is taken to mean a system which does not necessarily contain onlyaromatic or heteroaromatic groups, but in which a plurality of aromaticor heteroaromatic groups may also be interrupted by a short,non-aromatic unit (<10% of the atoms other than H, preferably <5% of theatoms other than H), such as, for example, an sp³-hybridised C, N or Oatom. Thus, for example, systems such as 9,9′-spirobifluorene,9,9-diarylfluorene, triarylamine, etc., should thus also be taken tomean aromatic ring systems for the purposes of this application.

For the purposes of this application, organic semiconductors arelow-molecular-weight, oligomeric, dendritic or polymeric, organic ororganometallic compounds which, as solid or as layer, havesemiconducting properties, i.e. in which the energy gap betweenconduction and valence band is between 1.0 and 3.5 eV. The term organicsemiconductor is applied here either to a pure component or a mixture oftwo or more components, at least one of which must have semiconductingproperties. In the case of the use of mixtures, however, it is notnecessary for each of the components to have semiconducting properties.For example, electronically inert compounds, such as, for example,polystyrene, can also be used together with semiconducting compounds.

In a preferred embodiment of the invention, the organic semiconductor isin the form of a mixture. In a further preferred embodiment of theinvention, the organic semiconductor is in the form of a copolymer.

For the purposes of the invention, a triplet emitter is taken to mean acompound which emits light from the triplet state, i.e. exhibitsphosphorescence instead of fluorescence in the electroluminescence,preferably an organometallic triplet emitter. This compound may inprinciple be of low molecular weight, oligomeric, dendritic orpolymeric. Without wishing to be tied to a specific theory, all emittingcompounds which contain the elements Ru, Os, Rh, Ir, Pd, Pt are referredto as triplet emitters for the purposes of this application.

In the case of the organic semiconductors according to the invention,there are various embodiments in which the units L=X or units of theformula (1) to (5) and/or the triplet emitter are either mixed into orcovalently bonded to the polymer.

One embodiment of the invention relates to mixtures BLEND1 comprising

-   (A) 5-99.9% by weight of at least one polymer POLY1; POLY1 comprises    1-100 mol %, preferably 5-80 mol %, particularly preferably 10-50    mol %, of one or more recurring units MONO1, where MONO1 contains at    least one structural unit L=X or a structural unit of the    formula (1) to (5),    and in addition-   (B) 0.1-95% by weight, preferably 0.5-80% by weight, particularly    preferably 1-50% by weight, in particular 2-25% by weight, of one or    more triplet emitters (TRIP1).

Although evident from the description, it should expressly be pointedout here that the recurring unit MONO1 which contains structural unitsL=X or the structural units of the formula (1) to (5) may also containmore than one such unit.

In the embodiment BLEND1, the triplet emitter (TRIP1) is non-covalentlymixed with the polymer POLY1. The recurring units MONO1 containingstructural elements L=X or units of the formula (1) to (5) arecovalently bonded to the polymer. The bonding here can in principle takeplace in any desired position, i.e. these units can be incorporated intoformula (1) to (5) via one or more positions at R¹ to R³ or optionallyvia R⁴, R⁵ and/or R⁶. Depending on the linking, these structural unitsare then incorporated into the main or side chain of the polymer.

A further embodiment of the invention relates to mixtures BLEND2comprising

-   (A) 0.5-99% by weight of at least one polymer POLY2; POLY2 comprises    0.5-100 mol % of one or more triplet emitters (TRIP2) covalently    bonded,    and in addition-   (B) 1-99.5% by weight of at least one compound COMP1 which contains    at least one structural unit L=X or at least one structural unit of    the formula (1) to (5) and which is capable of forming glass-like    layers, preferably having a glass transition temperature of above    70° C., at room temperature.

Although evident from the description of BLEND2, it should expressly bepointed out here that the compound COMP1 which contains structural unitsL=X or structural units of the formula (1) to (5) may also contain morethan one of these units.

The triplet emitter TRIP2 here may be incorporated into the main chainand/or into the side chain of the polymer POLY2.

A further aspect of this invention relates to mixtures BLEND3 comprising

-   (A) 0.5-98.9% by weight of at least one polymer POLY3;-   (B) 1-99% by weight of at least one compound COMP1 which contains at    least one structural unit L=X or at least one structural unit of the    formula (1) to (5) and is capable of forming glass-like layers,    preferably having a glass transition temperature of above 70° C., at    room temperature;    and in addition-   (C) 0.1-95% by weight, preferably 0.5-80% by weight, particularly,    preferably 1-50% by weight, in particular 2-25% by weight, of one or    more triplet emitters (TRIP1).

A further aspect of this invention relates to mixtures BLEND4 comprising

-   (A) 0.5-99% by weight of at least one polymer POLY3;    and in addition.-   (B) 1-99.5% by weight of a compound TRIP3; TRIP3 contains at least    one structural unit L=X or contains units of the formula (1) to (5)    covalently bonded to one or more triplet emitters, where at least    one group X is in free form, i.e. not coordinated to a metal atom;    this does not exclude further structural units L=X or structural    units of the formula (1) to (5) whose atom X is coordinated to a    metal atom (for example acetylacetonate ligands, etc.) being    present.

The invention furthermore relates to polymers POLY4 comprising

-   (A) 1-99.9 mol %, preferably 5-80 mol %, particularly preferably    10-50 mol %, of one or more recurring units MONO1 containing at    least one structural unit L=X, where the symbols L, X, R¹, R², R³,    R⁴, R⁵ and R⁶ have the same meaning as described above; and-   (B) 0.1-95 mol %, preferably 0.5-50 mol %, particularly preferably    1-25 mol %, of one or more triplet emitters TRIP2.

The proportion of triplet emitters in BLEND1 to BLEND4 and POLY4 mayalso be significantly lower than indicated above. A lower proportion oftriplet emitters may be preferred, in particular for the production ofwhite emission, as described in the unpublished application DE10343606.5.

The polymers POLY1 to POLY4 may be conjugated, partially conjugated,cross-conjugated or non-conjugated.

For the purposes of this invention, conjugated polymers are polymerswhose main chain contains principally sp²-hybridised (or alsosp-hybridised) carbon atoms, which may also be replaced by correspondinghetero atoms and whose units are conjugated with one another. In thesimplest case, this means the alternating presence of double and singlebonds in the main chain. It principally means that defects occurringnaturally (without further assistance) which result in conjugationinterruptions do not devalue the term “conjugated polymer”. Furthermore,conjugated in this application text likewise denotes the case whenarylamine units, arylphosphine units and/or certain heterocycles (i.e.conjugation via N, O, S or P atoms) and/or organometallic complexes,such as, for example, units as defined for TRIP2 (conjugation via themetal atom) are located in the main chain

For the purposes of this invention, partially conjugated polymers arepolymers which either contain relatively long conjugated sectionsinterrupted by non-conjugated sections in the main chain or whichcontain relatively long conjugated sections in the side chains of anon-conjugated polymer in the main chain.

For the purposes of this invention, cross-conjugated polymers arepolymers in which two conjugated sections are not conjugated with oneanother, but each individual one of these sections is conjugated with athird unit. This is the case, for example, if two conjugated sectionsare linked directly via a keto group, a sulfoxide group, a sulfone groupor a phosphine oxide group, but, for example, also in the case ofgeminal linking of two conjugated sections via a substituted orunsubstituted alkene group or in the case of linking of two conjugatedsections via, for example, a metaphenylene group.

By contrast, units, such as, for example, simple alkylene chains,(thio)ether bridges, ester, amide or imide links, would clearly bedefined as non-conjugated segments.

The polymers are preferably conjugated, partially conjugated orcross-conjugated.

In addition to the units MONO1 (in POLY1 and POLY4) and the tripletemitter TRIP2 (in POLY2 and POLY4), the polymers POLY1 to POLY4 maycontain various further structural elements. These may be, for example,structural units which are able to form the polymer skeleton orstructural units which influence the charge-injection orcharge-transport properties.

Such units are described in detail, for example, in WO 03/020790 and inthe unpublished application DE 10337346.2. The descriptions giventherein represent part of the present application by quote.

A suitable class of compound for cross-conjugated polymers POLY1 andPOLY4 are aromatic polyketones and aromatic polysulfones, each of whichmay be substituted for better solubility. An overview of these classesof compound is given by P. A. Staniland in “Comprehensive PolymerScience”, Ed. G. Allen, Volume 5, Chapter 29, 483-497, and F. Parodi,ibid., Chapter 33, 561-591. Aromatic polyphosphine oxides are likewisesuitable.

If the polymers POLY1 to POLY4 are non-conjugated polymers, in principleany desired classes of compound are suitable for this purpose so long asthe polymers, when processed as a blend, have sufficient solubility in asolvent or solvent mixture in which the other blend constituents arealso soluble, so that all components can be processed jointly fromsolution. Examples of non-conjugated polymers POLY1 and POLY4 whichcontain units L=X or units of the formula (1) to (5) covalently bondedare polycarboxylic acid derivatives in the broadest sense, such as, forexample, main-chain polyesters, side-chain polyesters, poly(glycolicacids), polylactic acids), poly(ε-caprolactones), polyacrylates,poly(hydroxybenzoic acids), poly(alkylene terephthalates),polycarboxylic anhydrides, polyamides, poly-(ε-caprolactams),polypeptides, polyaramids, polybenzamides, polyimides,poly(amide-imides), poly(ester-imides), poly(ether-imides), etc., butalso polymers such as, for example, polycarbonates,poly(ester-co-carbonates), poly(isocyanurates), polyurethanes orpolyester-polyurethanes. Preference is given here to polymers which haveat least one aromatic group, particularly preferably two aromaticgroups, bonded to the carbonyl group. Examples of main-chain polyesterswhich may be mentioned are, for example, poly(terephthalates). Examplesof side-chain polyesters which may be mentioned here are, for example,poly(acrylates), in particular poly(phenyl acrylates),poly(cyanoacrylates), poly(vinyl esters) or poly(vinyl acetates).Further non-conjugated polymers which contain units L=X covalentlybonded are, for example, side-chain polyphosphine oxides, polyetherketones (PEK), polyether sulfones, polysulfonamides, polysulfonimides,etc. Furthermore, for example, substituted or unsubstituted poly(vinylketones) are suitable, preferably aromatic polyvinyl ketones, or alsosubstituted or unsubstituted poly(vinylbenzophenones) or otherpolystyrene-analogous ketones, such as poly(4-benzoyl-α-methylstyrene).Polycarbazenes, such as polynitriles or polyisonitriles, are alsosuitable.

Examples of suitable non-conjugated polymers POLY3 which contain neitherunits L=X nor triplet emitters covalently bonded are, for example,polymers which are derived in the broadest sense from polyethylene orpolystyrene, but also electronically active, non-conjugated polymers,such as, for example, PVK (polyvinylcarbazole) or derivatives thereof.

The polymers POLY1, POLY2 and POLY3 may be homopolymers, i.e. they thencontain only one single monomer structure, but are generally copolymers.The polymer POLY4 is always a copolymer. The copolymers can have random,alternating or also block-like structures or alternatively have aplurality of these structures alternating. The polymers may likewisehave a linear or dendritic structure. The use of a plurality ofdifferent structural elements enables properties, such as, for example,solubility, solid-phase morphology, etc., to be adjusted.

The polymers POLY1 to POLY4 are prepared by polymerisation of one ormore monomers. In particular for the synthesis of conjugated orcross-conjugated polymers, some types which result in C—C links (SUZUKIcoupling, YAMAMOTO coupling, STILLE coupling) or in C—N links(HARTWIG-BUCHWALD coupling) have proven successful here. The way inwhich the polymerisation can be carried out by these methods and the wayin which the polymers can be separated off from the reaction medium andpurified is described, for example, in WO 03/048225 and WO 04/022626.

The synthesis of partially conjugated or non-conjugated polymers canalso be carried out by these methods by using corresponding monomerswhich are not conjugated throughout. For partially conjugated ornon-conjugated polymers, however, other synthetic methods, as aregenerally familiar from polymer chemistry, such as, for example,polycondensations, which result, for example, in ester or amide links,or cationic, anionic or free-radical polymerisations, which proceed, forexample, via the reaction of alkenes and result in the broadest sense inpolyethylene derivatives which contain the chromophores bonded in theside chains, are also suitable.

The following applies to preferred structural units of the formula (1)to (5):

-   X stands for O, S or N—R⁴;-   Y stands for P or As;-   Z stands for S or Se;-   R¹ to R⁶ are as defined above, where at least one of the    substituents R¹ to R³ on each structural unit of the formula (1)    to (5) represents an aromatic or heteroaromatic ring system having 1    to 40 C atoms, which may be substituted by one or more substituents    R⁴ or unsubstituted.

The following applies to particularly preferred structures of theformula (1) to (5):

-   X stands for O or N—R⁴; X very particularly preferably stands for O;-   Y stands for P;-   Z stands for S;-   R¹ to R⁶ are as defined above, where all substituents R¹ to R³ on    each structural unit of the formula (1) to (5) represent an aromatic    or heteroaromatic ring system having 1 to 40 C atoms, which may be    substituted by one or more substituents R⁴ or unsubstituted.

The substituents R¹ to R³ very particularly preferably contain aromaticor heteroaromatic ring systems in which at least one biphenyl-likestructure is bonded directly to the units of the formula (1) to (5),where, for example, fluorenes or spirobifluorenes are also intended tocount as such structures.

Structural units that have proven to be preferred structural units ofthe formula (1) to (5) are those whose radicals R¹ to R³ do not have aplanar structure. This is the case, in particular, if at least one ofthe substituents R¹ to R³ contains an sp³-hybridised carbon atom (orcorrespondingly also silicon, germanium, nitrogen, etc.) whichconsequently has approximately tetrahedral (or in the case of nitrogenpyramidal) geometry.

Preferred structural units are therefore units of the formula (1) toformula (5) in which at least one of the substituents R¹ to R³ containsat least one sp³-hybridised carbon atom.

In order to achieve clearer deviation from planarity, it is preferredfor this sp³-hybridised carbon atom to be a secondary, tertiary orquaternary carbon atom, particular preference is given to a tertiary orquaternary carbon atom, very particular preference is given to aquaternary carbon atom. A secondary, tertiary or quaternary carbon atomis taken to mean a carbon atom having two, three or four non-hydrogensubstituents respectively.

Particular preference is given to structural units of the formula (1) toformula (5) which contain a 9,9′-spirobifluorene derivative, a9,9-disubstituted fluorene derivative, a 6,6- and/or 12,12-di- ortetra-substituted indeno-fluorene derivative, a triptycene derivative(preferably linked via position 9 and/or 10) or a tetraarylmethanederivative in at least one of the radicals R¹ to R³. Very particularpreference is given to structural units of the formula (1) to (5) whichcontain a 9,9′-spirobifluorene derivative in at least one of theradicals R¹ to R³.

Polymers containing 9,9′-spirobifluorene derivatives and at the sametime structural units of one or more of the formulae (1) to (5) arenovel and are therefore likewise a subject-matter of the presentinvention.

Examples of particularly preferred recurring units MONO1 or compoundsCOMP1 which contain structural units of the formulae (1) to (5) aresubstituted or unsubstituted structures of the formulae (6) to (148)shown, where the dashed single bonds denote a possible link in thepolymer (MONO1) or links for molecular extension (COMP1); Ph stands fora substituted or unsubstituted phenyl group and alkyl stands for astraight-chain, branched or cyclic alkyl chain, which may be substitutedor unsubstituted and in which one or more H atoms may be replaced byfluorine. These structural elements of the formulae (6) to (148) arealso preferably a constituent of the compounds TRIP3, which represent acombination of triplet emitters and units of the formula (1) to (5).Potential substituents R⁴ are generally not shown owing to betterclarity:

Although evident from the description, it should again explicitly bepointed out here that the structural units of the formulae (6) to (148)may also be asymmetrically substituted, i.e. that different substituentsR⁴ may be present on a unit, or they may also be bonded in differentpositions.

The recurring units MONO1 are covalent constituent of POLY1 and POLY4.It has been found that a proportion of these recurring units in therange 5-100 mol % (based on all recurring units in the polymer) achievesgood results here. A proportion of 5-100 mol % of recurring units MONO1is preferred for POLY1. A proportion of 10-80 mol % of recurring unitsMONO1 is particularly preferred, a proportion of 10-50 mol % ofrecurring units MONO1 is very particularly preferred.

Compounds COMP1 are mixture constituent of BLEND2 and BLEND3. It hasbeen found that a proportion of these compounds in the mixture in therange 5-99% by weight achieves good results here. A proportion of 5-99%by weight of compounds COMP1 is thus preferred for BLEND2 and BLEND3. Aproportion of 10-80% by weight of COMP1 is particularly preferred, aproportion of 10-50% by weight of COMP1 is very particularly preferred.

A further preferred embodiment is the mixture BLEND5, which is formed bymixing compounds COMP1 into BLEND1, so that structural units L=X orunits of the formula (1) to (5) here are both covalently bonded to thepolymer and also mixed in. It has been found here that a totalproportion of 5-99 mol % of structural units of these formulae achievesgood results, irrespective of whether these units are covalently bondedto the polymer or are mixed in. A total proportion of 5-99 mol % ofstructural units L=X or units of the formulae (1) to (5) is thuspreferred here. A total proportion of 10-80 mol % of structural unitsL=X or units of the formulae (1) to (5) is particularly preferred, atotal proportion of 10-50 mol % of structural units of the formulae (1)to (5) is very particularly preferred.

A further preferred embodiment is the mixture BLEND6, which is formed bymixing compounds COMP1 into BLEND4, so that structural units L=X orunits of the formula (1) to (5) here are both covalently bonded to thetriplet emitter and also mixed in. Here too, it has been found that atotal proportion of 5-99 mol % of these structural units achieves goodresults, irrespective of whether these units are covalently bonded tothe triplet emitter or are mixed in. A total proportion of 5-99 mol % ofstructural units L=X or units of the formulae (1) to (5) is thuspreferred here. A total proportion of 10-80 mol % of structural unitsL=X or units of the formulae (1) to (5) is particularly preferred, atotal proportion of 10-50 mol % of structural units L=X or units of theformulae (1) to (5) is very particularly preferred.

A further preferred embodiment is the mixture BLEND7, which is formed bymixing compounds COMP1 and/or triplet emitters TRIP1 into POLY4.

The triplet emitters TRIP1 mixed into BLEND1 and BLEND3, or the tripletemitters TRIP2 copolymerised into POLY2 (=BLEND2), or the tripletemitters TRIP3 mixed into BLEND4 can be selected from any desiredorganic, organometallic or inorganic classes of substance which are ableto emit light from the triplet state at room temperature, i.e. exhibitphosphorescence instead of fluorescence: these are firstly, inparticular, compounds which contain heavy atoms, i.e. atoms from thePeriodic Table of the Elements having an atomic number of greater than36. Particularly suitable for this purpose are compounds which contain dand f transition metals which satisfy the above-mentioned condition.Very particular preference is given here to corresponding structuralunits which contain elements from group 8 to 10 (i.e. Ru, Os, Rh, Ir,Pd, Pt). Particular preference is given to triplet emitters based ontris-ortho-metallated metal complexes.

The triplet emitters TRIP1 and TRIP3 can be low-molecular-weight,oligomeric, dendritic or polymeric compounds. Since they are in somecases processed as mixture constituent (BLEND1, BLEND3 or BLEND4),adequate solubility in suitable solvents (for example toluene, xylene,anisole, THF, methylanisole, methylnaphthalene or mixtures of thesesolvents) must exist in order that processing from solution is possible.Suitable low-molecular-weight structural units here are variouscomplexes which are described, for example, in the applicationspecifications WO 02/068435, WO 02/081488, EP 1239526 and WO 04/026886.In particular, the halogenated complexes described in WO 02/068435 arealso suitable as starting compound for TRIP3, since the halogenfunctionality allows easy derivatisation of the complexes withstructural units of the formula (1) to (5). Suitable dendrimerstructures for TRIP1 and TRIP3 are complexes as described, for example,in WO 99/21935, WO 01/059030 and WO 02/066552.

The triplet emitter TRIP2 is incorporated covalently into the polymerchain of POLY2 (BLEND2), In order to facilitate the incorporation ofTRIP2 into POLY2, functional polymerisable groups must be present onTRIP2. Examples of corresponding brominated complexes which can beemployed as monomers in polymerisation reactions, for example inaccordance with Suzuki or in accordance with Yamamoto, are described inWO 02/068435 and in the unpublished application DE 10350606.3.

The mixture BLEND1 according to the invention is obtained by admixing atriplet emitter TRIP1 with the polymer POLY1.

The mixture BLEND2 according to the invention is obtained by admixingcompound COMP1 containing structural units L=X or structural units ofthe formula (1) to (5) with the polymer POLY2.

The mixture BLEND3 according to the invention is obtained by admixingcompound COMP1 containing structural units L=X or structural units ofthe formula (1) to (5) and a triplet emitter TRIP1 with the polymerPOLY3. The mixture BLEND4 according to the invention is obtained byadmixing units TRIP3 with the polymer POLY3.

It may additionally be preferred also to mix further conjugated,partially conjugated, cross-conjugated or non-conjugated polymers,oligomers, dendrimers or further low-molecular-weight compounds intoBLEND1 to BLEND7. The addition of further components may proveappropriate for some applications: for example, addition of anelectronically active substance enables the hole or electron injection,the hole or electron transport or the charge equilibrium in thecorresponding blend to be regulated. The added component may also makesinglet-triplet transfer easier. However, the addition of electronicallyinert compounds may also be helpful in order, for example, to controlthe viscosity of a solution or the morphology of the film formed. Theinvention likewise relates to the blends obtained in this way.

BLEND1 to BLEND7 are prepared as follows: the individual constituents ofthe blend are combined in a suitable mixing ratio and dissolved in asuitable solvent. Suitable solvents are, for example, toluene, anisole,xylenes, methylanisole, methylnaphthalene, chlorobenzene, cyclic ethers(for example dioxane, THF, methyldioxane), amides (for example NMP, DMF)or mixtures of these solvents. Alternatively, the constituents of theblend may also be dissolved individually. In this case, the solution ofthe blend is obtained by combining the individual solutions in asuitable mixing ratio. The dissolution process here is preferablycarried out in an inert atmosphere and optionally at elevatedtemperature. The blend is usually not isolated as a solid (byre-precipitation), but instead is processed further directly fromsolution; however, the invention also relates to blends which have beenprecipitated once again.

A suitable ratio of the individual components is, for example, a mixturewhich comprises a total of 1-99.5 mol %, preferably 5-99 mol %,particularly preferably 10-80 mol %, in particular 10-50 mol %, of unitsL=X or units of the formula (1) to (5) (MONO1 in POLY1 or COMP1) and0.1-95 mol %, preferably 0.5-80 mol %, particularly preferably 1-50 mol%, in particular 2-25 mol %; of TRIP1, TRIP2 and TRIP3, where the dataare based on all the units present (blend constituents or recurringunits in the polymer). This is independent of whether the components arecovalently bonded to a polymer or mixed in.

The organic semiconductors according to the invention, i.e. the mixturesBLEND1 to BLEND7 and polymers POLY4 according to the invention, have,inter alia, the following surprising advantages over the above-mentionedprior art:

-   -   The solubility in organic solvents is generally better than the        solubility of the polymers and mixtures in accordance with the        prior art. The better solubility offers an advantage, for        example over bridged carbazole units, which are mentioned as        closest prior art, since the maximum carbazole proportion        therein is frequently determined by the poor solubility, but in        some cases a higher carbazole proportion would be desirable for        further improvement of the device properties.    -   The chemical accessibility of the units of the formula (1) to        (5), both as blend constituent and also as monomer, is not        problematic. In some cases, these blend constituents and        monomers are also commercially available. This is a crucial        advantage over, for example, the bridged carbazole units (DE        10328627.6), the synthesis and purification of which are        considerably more complex.    -   The mixtures and polymers according to the invention exhibit        higher oxygen stability than mixtures and polymers in accordance        with the prior art. This simplifies the preparation of these        compounds and mixtures and also their processing, which        represents a considerable practical advantage.    -   The efficiency of light emission of the triplet emitter is        better in the organic semiconductors according to the invention        compared with polymers and mixtures in accordance with the prior        art.    -   The lifetime of the devices according to the invention is better        than in devices in accordance with the prior art.

The organic semiconductors according to the invention, i.e. the mixturesBLEND1 to BLEND7 or the polymers POLY4, can be used in PLEDs, inparticular as electroluminescent materials (emitting materials). PLEDsare generally constructed using a general process which iscorrespondingly to be adapted to the individual case. A process of thistype has been described in detail, for example, in WO 04/037887.

The invention therefore also relates to the use of an organicsemiconductor according to the invention, i.e. a mixture BLEND1 toBLEND7 according to the invention or a polymer POLY4 according to theinvention, in a PLED as electroluminescent material.

The invention thus likewise relates to a PLED having one or more layers,where at least one of these layers comprises one or more organicsemiconductors according to the invention, i.e. one or more mixturesBLEND1 to BLEND7 according to the invention or polymers POLY4 accordingto the invention.

The present application text and the following examples are directed tothe use of organic semiconductors according to the invention, i.e.mixtures BLEND1 to BLEND7 or polymers POLY4 according to the invention,in relation to PLEDs and the corresponding displays. In spite of thisrestriction of the description, it is readily possible for the personskilled in the art, without inventive step, also to use the polymers orblends according to the invention for further uses in other electronicdevices, for example for organic solar cells (O-SCs), non-linear opticsor also organic laser diodes (O-lasers), to mention but a fewapplications. The present invention also relates to these.

The invention is explained in greater detail by the following exampleswithout wishing to be restricted thereby.

EXAMPLES Example 1 Synthesis of the Comonomers for the Polymers

The synthesis of the comonomers used for conjugated polymers isdescribed in detail in WO 02/077060 and the literature cited therein,and in the unpublished application DE 10337346.2. The monomers M1 to M5and M8 used below will be shown again here for reasons of clarity:

Example 2 4,4′-Dibromobenzophenone (monomer M6 of the Formula (1))

4,4′-Dibromobenzophenone was obtained from Fluka in a purity of 98% andpurified by further recrystallisation from ethanol to a purity of 99.7%(according to HPLC).

Example 3 Synthesis of bis(4-bromophenyl)phenylphosphine oxide (monomerM7 of the formula (3)) a) Synthesis of bis(4-bromophenyl)phenylphosphine

33.9 g (144 mmol) of dibromobenzene were dissolved in 300 ml of dry THFin a dry 1000 ml four-necked flask with internal thermometer, stirrerbar, argon blanket and 2 dropping funnels and cooled to −70° C. 90 ml(144 mmol) of n-butyllithium (1.6 M in hexane) were added dropwise overthe course of 30 min., and the mixture was stirred at this temperaturefor a further 1 h. 12.9 g (9.75 ml, 72 mmol) of dichlorophenylphosphinein 60 ml of dry THF were then added dropwise at this temperature. Themixture was allowed to come to room temperature overnight. 20 ml ofmethanol were added, and the batch was evaporated to dryness. Theresidue was taken up in dichloromethane, filtered, and the solvent wasremoved under reduced pressure. The compound was employed for thefollowing reaction without further purification.

b) Synthesis of bis(4-bromophenyl)phenylphosphine oxide (monomer M7)

10.05 g (24 mmol) of bis(4-bromophenyl)phenylphosphine were dissolved in200 ml of ethyl acetate in a 500 ml four-necked flask with internalthermometer, mechanical stirrer, reflux condenser and dropping funneland cooled to an internal temperature of 5° C. A solution of 2.25 ml(26.4 mmol) of H₂O₂ (35%) in 17.5 ml of water was added dropwise overthe course of 30 min., and the mixture was stirred at room temperaturefor a further 12 h. 25 ml of saturated sodium sulfite solution weresubsequently added, the organic phase was separated off, washed twicewith saturated sodium sulfite solution and dried over sodium sulfate.The solvent was removed under reduced pressure. The purification wascarried out firstly by column chromatography on silica using a solventmixture of initially hexane:ethyl acetate 2:1 to hexane:ethyl acetate1:1. Further purification was carried out by recrystallisation fromheptane/toluene, giving 6.5 g of product in a purity of 99.7% (accordingto HPLC). ¹H-NMR (500 MHz, CDCl₃): [ppm] 7.46-7.66 (m). ³¹P-NMR (CDCl₃):[ppm] 28.40.

Example 4 Synthesis of2,7-dibromo-9-keto-10-(2-ethylhexyl)-10-methoxydihydrophenanthrene(monomer M9 of the formula (1)) a) Synthesis of2,7-dibromo-9-keto-10-(2-ethylhexyl)-10-hydroxydihydrophenanthrene

4.6 g (185 mmol) of magnesium were introduced into a 500 ml four-neckedflask with reflux condenser, mechanical stirrer, internal thermometer,argon blanket and dropping funnel. The apparatus was dried by heating, agrain of iodine was added, then 37.6 ml (185 mmol) of ethylhexyl bromidein 175 ml of absolute THF were added dropwise. The mixture was heatedunder reflux until all the magnesium was consumed. After cooling to roomtemperature, the Grignard solution was transferred into a droppingfunnel. 45 g (123 mmol) of dibromophenanthrenequinone were suspended at0° C. in 300 ml of THF in a 1000 ml four-necked flask with mechanicalstirrer, internal thermometer, reflux condenser, dropping funnel andargon blanket. The Grignard solution was added dropwise to thissuspension at such a rate that the internal temperature did not exceed25° C. The mixture was subsequently stirred overnight at roomtemperature. 200 ml of saturated NH₄Cl soln. were added to the batch.Ethyl acetate was added, the mixture was extracted twice with saturatedNaCl soln. and dried over Na₂SO₄, and the solvent was removed. Theresidue was boiled up in 250 ml of hexane, the green solid was filteredoff, and the product was crystallised out. The yield was 39.3 g (67% oftheory). ¹H-NMR (CDCl₃): [ppm]=8.03 (m, 1H), 7.91 (m, 1H), 7.78 (m, 2H),7.62 (m, 1H), 7.52 (m, 1H), 3.91. (s, exchangeable with D₂O, 1H), 1.72(m, 2H), 1.33 (m, 1H), 1.10 (m, 8H), 0.81 (m, 3H), 0.65 (m, 3H).

b) Synthesis of2,7-dibromo-9-keto-10-(2-ethylhexyl)-10-methoxydihydrophenanthrene(monomer M9)

3.3 g (81.5 mmol) of NaH (60% dispersion in mineral oil) in 30 ml ofDMSO were introduced into a 500 ml four-necked flask with mechanicalstirrer, condenser, thermometer and dropping funnel which had been driedby heating. 21.6 g (54.3 mmol) of2,7-dibromo-9-keto-10-(2-ethylhexyl)-10-hydroxydihydrophenanthrene in 60ml of DMSO were slowly added dropwise, and the mixture was stirred atroom temperature for 30 min. 5.1 ml (81.5 mmol) of methyl iodide werethen added dropwise over the course of 1 h with ice cooling. The mixturewas stirred at room temperature for 2-days, then cooled to 5° C., 90 mlof semi-conc. NH₄OH were added dropwise, 100 ml of MeOH were addeddropwise, the mixture was stirred in an ice bath for 30 min, and theproduct was filtered off with suction, washed with MeOH and dried at 60°C. in a vacuum drying cabinet. The crude product was recrystallised anumber of times from methanol. The total yield was 17.3 g (65% oftheory) with a purity of >99.8%. ¹H-NMR (CDCl₃): [ppm]=8.16 (d,⁴J_(HH)=2.3 Hz, 1H), 7.78 (m, 4H), 7.56 (dd, ³J_(HH)=8.7 Hz, ⁴J_(HH)=2.3Hz, 2H), 3.17 (s, 3H), 1.71 (m, 2H), 1.26 (m, 1H), 1.06 (m, 8H), 0.77(m, 3H), 0.59 (m, 3H).

Example 5 Synthesis of2,7-dibromo-9-keto-10,10-bis(4-tert-butylphenyl)dihydrophenanthrene(monomer M10 of the formula (1))

200 mg of para-toluenesulfonic acid and 10 g (15.8 mmol) of2,7-dibromo-9,10-bis(4-tert-butylphenyl)-9,10-dihydroxydihydrophenanthrenewere suspended in 80 ml of toluene in a 250 ml round-bottomed flask withmagnetic stirrer and water separator with condenser and boiled on thewater separator for 3 h. The precipitate was filtered off with suction,washed with methanol, recrystallised twice from toluene and dried underreduced pressure. The yield was 6.3 g (65% of theory) with a purityof >99.9%. ¹H-NMR (CDCl₃): [ppm]=8.06 (d, ⁴J_(HH)=2.0 Hz, 1H), 7.80 (d,³J_(HH)=8.7 Hz, 1H), 7.73 (d, ³J_(HH)=8.7 Hz, 1H), 7.68 (dd, ³J_(HH)=8.4Hz, ⁴J_(HH)=2.0 Hz, 1H), 7.55 (dd, ³J_(HH)=8.3 Hz, ⁴J_(HH)=2.0 Hz, 1H),7.26 (m, 4H), 6.91 (d, ⁴J_(HH)=2.0 Hz, 1H), 6.83 (m, 4H), 1.26 (s, 18H).

Example 6 Blend Constituents V1 and V2 (COMP1 of the Formula (1))

As blend constituent V1, use was made by way of example of the followingketone, the synthesis of which has already been described in DE10317556.3:

As blend constituent V2, use was made by way of example of the followingphosphine oxide, the synthesis of which is described in DE 10330761.3:

Example 7 Structural Units TRIP1 for Use in Blends

The compounds TRIP1 used here by way of example are derivatives oftris(phenylpyridyl)iridium(III). The synthesis of these compounds hasalready been described in WO 02/081488 and WO 04/026886. For clarity,the iridium complexes used here are depicted again below:

Example 8 Further Blend Constituents

As further blend constituents, use was made of the spirotriarylaminederivative amine1 and the spirooxadiazole derivative Ox1, the structuresof which are shown below:

Example 9 Synthesis of Conjugated Polymers POLY3

The synthesis of conjugated polymers POLY3 which contain no units of theformula (1) to (5) and no compounds TRIP2 has already been described,for example, in the application specifications WO 02/077060, WO03/020790 and WO 04/070772.

Example 10 Synthesis of Polymer P1

The synthesis was carried out in accordance with the process describedin WO 03/048224. The following were employed: 1.6013 g (2 mmol) ofmonomer M1, 0.8118 g (1.2 mmol) of monomer M2, 0.3035 g (0.4 mmol) ofmonomer M5, 0.1744 g (0.4 mmol) of monomer M7 and 2.03 g (2.2equivalents) of potassium phosphate hydrate in 19 ml of dioxane, 6 ml oftoluene and 12 ml of H₂O. The following were used as catalyst: 0.45 mgof Pd(OAc)₂ and 3.65 mg of P(o-tolyl)₃. Work-up gave 1.57 g of polymerhaving a molecular weight M_(n) of 58,000 g/mol and M_(w) of 185,000g/mol (GPC in THF using polystyrene standard).

Example 11 Synthesis of Polymer P2

The synthesis was carried out in accordance with the process describedin WO 03/048224. The following were employed: 1.2889 g (2 mmol) ofmonomer M3, 0.7951 g (1.2 mmol) of monomer M4, 0.3035 g (0.4 mmol) ofmonomer M5, 0.1360 g (0.4 mmol) of monomer M6 and 2.03 g (2.2equivalents) of potassium phosphate hydrate in 19 ml of dioxane, 6 ml oftoluene and 12 ml of H₂O. The following were used as catalyst: 0.45 mgof Pd(OAc)₂ and 3.65 mg of P(o-tolyl)₃. Work-up gave 1.72 g of polymerhaving a molecular weight M_(n) of 87,000 g/mol and M_(w) of 219,000g/mol (GPC in THF using polystyrene standard).

Example 12 Non-Conjugated Polymers (POLY1) P6 and P7

Polystyrene P6 having a melt flow index of 7.5 was purchasedcommercially from Aldrich. The synthesis of poly(vinylbenzophenone) P7was carried out in accordance with Helv. Chim. Acta 1999, 82, 338-346.

Example 13 Preparation of the Blends

The mixtures were prepared by dissolving the blend constituents in thedesired ratio and in the desired concentration in toluene. Thedissolution process was carried out at 60° C. in an inert atmosphere.The solution was processed directly without isolation of the mixture(re-precipitation of the solid components).

Example 14 Production of the Polymeric Light-Emitting Diodes (PLEDs)

The way in which PLEDs can be produced is described in detail, forexample, in WO 04/037887 and the literature cited therein. It has beenfound here that the polymers and blends according to the invention formmore homogeneous films than the polymers and blends in accordance withthe prior art. Without wishing to be tied to a particular theory, weassume that this is due to the better solubility of these compounds.

Example 15 Overview of the Polymers Synthesised and Used

Table 1 gives an overview of the composition of some of the polymerssynthesised and used in the devices.

TABLE 1 Overview of the composition of some polymers Polymer Monomers P150% of M1 30% of M2 10% of M5 10% of M7 P2 50% of M1 30% of M8 10% of M510% of M7 P3 50% of M1 30% of M2 10% of M5 10% of M6 P4 50% of M1 30% ofM2 10% of M5 10% of M9 P5 50% of M1 50% of M6 P6 50% of M1 50% of M7 P7polystyrene

Example 16 Device Examples

Table 2 gives an overview of various blends of polymers and tripletemitters, optionally with further components.

TABLE 2 Some device results with blends according to the inventionTriplet Further U @ Blend Polymer^(a) emitter^(b) constituents^(a) Max.eff. 100 cd/m² CIE x/y^(c) Lifetime^(d) Blend 1 a) P1 20% of Ir2 13.55cd/A  5.0 V 0.62/0.38 1000 h Blend 1 b) P1 8% of Ir3 3.69 cd/A 5.0 V0.68/0.32  710 h Blend 2 a) P2 20% of Ir2 10.56 cd/A  4.4 V 0.62/0.385900 h Blend 2 b) P2 8% of Ir3 4.13 cd/A 4.5 V 0.68/0.32 1140 h Blend 3P3 8% of Ir2 8.79 cd/A 5.8 V 0.68/0.32  830 h Blend 4 P4 20% of Ir2 5.89cd/A 6.5 V 0.62/0.38 2500 h Blend 5 P5 8% of Ir3 3.08 cd/A 5.7 V0.68/0.32  480 h Blend 6 a) P6 8% of Ir1 7.49 cd/A 6.0 V 0.42/0.56  420h Blend 6 b) P6 20% of Ir1 20.0 cd/A 4.5 V 0.40/0.58 2000 h Blend 6 c)P6 20% of Ir2 6.51 cd/A 5.7 V 0.62/0.38 >10000 h  Blend 7 a) 30% of P78% of Ir1 30% of V1 26.78 cd/A  4.7 V 0.41/0.57 2800 h 20% of V2 20% ofamine1 Blend 7 b) 30% of P7 8% of Ir1 30% of V1 27.40 cd/A  4.1 V0.38/0.59 not stated 20% of amine1 20% of Ox1 ^(a)The proportion of thepolymer or the further blend constituents is based on the totalcomposition of all constituents apart from the triplet emitter. ^(b)Theproportion of the triplet emitter is based on the matrix, i.e. thepolymer or the mixture of the polymer with the other constituents.^(c)CIE coordinates: chromaticity coordinates of the CommissionInternationale de I'Eclairage from 1931. ^(d)The stated lifetime isbased on the so-called LT50 value, i.e. the time which passes until thecorresponding PLED only has 50% of the initial brightness; the valueswere determined with an initial brightness of 100 cd/m².

1. An organic semiconductor comprising (A) at least one non-conjugatedpolymer, (B) at least one structural unit L=X, where the followingapplies to the symbols used: L is on each occurrence, identically ordifferently, (R¹)(R²)C, (R¹)P, (R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P,(R¹)(R²)(R³)As, (R¹)(R²)(R³)Sb, (R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se,(R¹)(R²)Te, (R¹)(R²)S(═O), (R¹)(R²)Se(═O) or (R¹)(R²)Te(═O); X is oneach occurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X is not S or Se if L stands for S, Se or Te; R¹, R², R³ ison each occurrence, identically or differently, H, F, CN, astraight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 C atoms, which is optionally substituted by R⁵ or mayalso be unsubstituted, where one or more non-adjacent CH₂ groups may bereplaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se,C═NR⁶, —O—, or —S— and where one or more H atoms are optionally replacedby F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which is optionally substituted by one or moreradicals R⁵, where two or more substituents R¹, R² and/or R³ may alsowith one another form a mono- or polycyclic, aliphatic or aromatic ringsystem; all substituents R¹ to R³ on one structural unit here must notbe H or F; the groups R¹ to R³ may furthermore optionally have bonds tothe polymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms replaced byfluorine, an aryl, heteroaryl or aryloxy group having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁶, or OH orN(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴ or CN,B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically or differently,H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 Catoms; and (C) at least one triplet emitter; with the proviso thatmixtures of two polymers in which the first polymer contains covalentlybonded triplet emitters and the other is a copolymer comprising TPDunits and diphenyl sulfone ether or diphenyl ketone ether units areexcluded; and furthermore with the proviso that polymers containing onthe one hand covalently bonded triplet emitters and on the other handunits of the formula (a) are excluded from the invention:

in which Ar¹ and Ar² each independently denote a tetravalent aromatichydrocarbon group or a tetravalent heterocyclic group; one of the unitsX¹ and X² denotes C(═O) or C(R¹)(R²) and the other denotes O, S, C(═O),S(═O), SO₂, Si(R³)(R⁴), N(R⁵), B(R⁶), P(R⁷) or P(═O)(R⁸); where theradicals R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ in the formula (a) eachindependently denote a hydrogen atom, a halogen atom, an alkyl group, analkoxy group, an alkylthio group, an alkylamino group, an aryl group, anaryloxy group, an arylthio group, an arylamino group, an arylalkylgroup, an arylalkoxy group, an arylalkylthio group, an arylalkylaminogroup, an acyl group, an aryloxy group, an amide group, an imine group,a substituted silyl group, a substituted silyloxy group, a substitutedsilylthio group, a substituted silylamino group, a monovalentheterocyclic group, an arylalkenyl group, an arylethynyl group or acyano group, M denotes a group which is represented by formula (b),formula (c) or formula (d)—Y¹—Y²—  formula (b) in which Y¹ and Y² each independently denote O, S,C(═O), S(═O), SO₂, C(R⁹)(R¹⁰), Si(R¹¹)(R¹²), N(R¹³), B(R¹⁴), P(R¹⁵) orP(═O)(R¹⁶), where the radicals R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶,in the formula (b) each independently denote a hydrogen atom, a halogenatom, an alkyl group, an alkoxy group, an alkylthio group, an alkylaminogroup, an aryl group, an aryloxy group, an arylthio group, an arylaminogroup, an arylalkyl group, an arylalkoxy group, an arylalkylthio group,an arylalkylamino group, an acyl group, an acyloxy group, an amidegroup, an imine group, a substituted silyl group, a substituted silyloxygroup, a substituted silylthio group, a substituted silylamino group, amonovalent heterocyclic group, an arylalkenyl group, an arylethynylgroup or a cyano group, where Y¹ and Y² are not identical if Y¹ is notC(R⁹)(R¹⁰) or Si(R¹¹)(R¹²).]—Y³═Y⁴—  formula (c) in which Y³ and Y⁴ each independently denote N, B,P, C(R¹⁷) or Si(R¹⁸); the radicals R¹⁷ and R¹⁸ in the formula (c) eachindependently denote a hydrogen atom, a halogen atom, an alkyl group, analkoxy group, an alkylthio group, an alkylamino group, an aryl group, anaryloxy group, an arylthio group, an arylamino group, an arylalkylgroup, an arylalkoxy group, an arylalkylthio group, an arylalkylaminogroup, an acyl group, an acyloxy group, an amide group, an imine group,a substituted silyl group, a substituted silyloxy group, a substitutedsilylthio group, a substituted silylamino group, a monovalentheterocyclic group, an arylalkenyl group, an arylethynyl group or acyano group;—Y⁵—  formula (d) in which Y⁵ denotes O, S, C(═O), S(═O), SO₂,C(R¹⁹)(R²⁰), Si(R²¹)(R²²), N(R²³), B(R²⁴), P(R²⁵) or P(═O)(R); where theradicals R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵ and R²⁶ in the formula (d)each independently denote a hydrogen atom, a halogen atom, an alkylgroup, an alkoxy group, an alkylthio group, an alkylamino group, an arylgroup, an aryloxy group, an arylthio group, an arylamino group, anarylalkyl group, an arylalkoxy group, an arylalkylthio group, anarylalkylamino group, an acyl group, an acyloxy group, an amide group,an imine group, a substituted silyl group, a substituted silyloxy group,a substituted silylthio group, a substituted silylamino group, amonovalent heterocyclic group, an arylalkenyl group, an arylethynylgroup or a cyano group; Z₁ denotes —CR³⁶═CR³⁷— or —C≡C—; R³⁶ and R³⁷each independently denote a hydrogen atom, an alkyl group, an arylgroup, a monovalent heterocyclic group or a cyano group; d denotes 0or
 1. 2. The organic semiconductor according to claim 1, wherein thestructural units L=X are selected from the formulae (1) to (5)

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹ R⁶, have thesame meaning as described under claim
 1. 3. The organic semiconductoraccording to claim 2, wherein they comprise at least 0.5% by weight ofat least one non-conjugated polymer, at least 1% by weight of at leastone structural unit L=X or a structural unit of the formulae (1) to (5)and at least 0.1% by weight of at least one triplet emitter.
 4. Theorganic semiconductor according to claim 2, wherein the at least onepolymer is a polymer (POLY1 to POLY4) wherein (POLY1) comprises 1-100mol % of one or more recurring units (MONO1) containing at least onestructural unit L=X or at least one structural unit of the formula (1)to (5); (POLY2) comprises 0.5-99.5 mol % of one or more triplet emitters(TRIP2) covalently bonded; (POLY3) is at least one non-conjugatedpolymer; (POLY4) comprising (A) 1-99.9 mol % of one or more recurringunits MONO1 containing at least one structural unit L=X, where symbolsL, X, R¹, R², R³, R⁴, R⁵ and R⁶ have the same meaning as described underclaim 1; (B) 0.1-95 mol % of one or more triplet emitters TRIP2.
 5. Theorganic semiconductor according to claim 4, wherein the polymers POLY1to POLY4 contain further structural elements of at least group 1 togroup 4 group 1: units which significantly increase the hole injectionor transport properties of the polymers; group 2: units whichsignificantly increase the electron injection or transport properties ofthe polymers; group 3: units which comprise combinations of individualunits of group 1 and group 2; group 4: units which alter the emissioncharacteristics so that phosphorescence can be obtained instead offluorescence.
 6. The organic semiconductor as claimed in claim 5,wherein group 1 is a compound of the formulae (II)-(XIX)

wherein R¹ is identical or different on each occurrence and is in eachcase a linear, branched or cyclic alkyl or alkoxy chain which has from 1to 22 carbon atoms and in which one or more nonadjacent carbon atoms mayalso be replaced by N—R⁵, O, S, —CO—O—, O—CO—O, where one or more Hatoms may also be replaced by fluorine, or is an aryl or aryloxy groupwhich has from 5 to 40 carbon atoms and in which one or more carbonatoms may also be replaced by O, S or N, which may also be substitutedby one or more nonaromatic radicals R¹, or is Cl, F, CN, N(R⁵)₂, N(R⁵)₃⁺, where two or more radicals R¹ may also together form a ring system;R² is identical or different on each occurrence and is in each case alinear, branched or cyclic alkyl or alkoxy chain which has from 1 to 22carbon atoms and in which one or more nonadjacent carbon atoms may alsobe replaced by N—R⁵, O, S, —CO—O—, O—CO—O, where one or more H atoms mayalso be replaced by fluorine, or is an aryl or aryloxy group which hasfrom 5 to 40 carbon atoms and in which one or more carbon atoms may alsobe replaced by O, S or N which may also be substituted by one or morenonaromatic radicals R¹, or is CN; R⁴ and R³ is identical or differenton each occurrence and are each H, a linear, branched or cyclic alkylchain which has from 1 to 22 carbon atoms and in which one or morenonadjacent carbon atoms may also be replaced by N—R⁵, O, S, —CO—O—,O—CO—O, where one or more H atoms may also be replaced by fluorine, orare each an aryl group which has from 5 to 40 carbon atoms and in whichone or more carbon atoms may also be replaced by O, S or N, which mayalso be substituted by one or more nonaromatic radicals R¹, or are eachCN; where a plurality of adjacent radicals R³ and/or R⁴ may togetheralso form a ring; R⁵ is identical or different on each occurrence and isin each case H, a linear, branched or cyclic alkyl chain which has from1 to 22 carbon atoms and in which one or more nonadjacent carbon atomsmay also be replaced by O, S, —CO—O—, O—CO—O, where one or more H atomsmay also be replaced by fluorine, or is an aryl group which has from 5to 40 carbon atoms and in which one or more carbon atoms may also bereplaced by O, S or N, which may also be substituted by one or morenonaromatic radicals R′; m is identical or different on each occurrenceand is in each case 0, 1, 2, or 3; n is identical or different on eachoccurrence and is in each case 0, 1, 2, 3 or 4, Ar¹, Ar², Ar³ areidentical or different on each occurrence and are aromatic orheteroaromatic hydrocarbons which have from 2 to 40 carbon atoms and maybe substituted by one or more nonaromatic radicals R¹; o is 1, 2 or 3,and group 2 is a compound of the formulae (XX) to (XXX),

where the symbols R¹ and indices m and n are as defined above and p is0, 1 or 2, and group 3 is a compound of the formulae (XXXI) to (XXXXVI),

where the symbols Ar¹, R¹, R², R³, R⁴, R⁵and the indices m, n, o and pare as defined above and Z is identical or different on each occurrenceand is in each case a single chemical bond, a CR³R⁴ group, a—CR³R⁴—CR³R⁴— group, a —CR³═CR⁴— group, O, S, N—R⁵, C═O, C═CR³R⁴ orSiR³R⁴; and group 4 is a compound of the formulae (XXXXVII) to (XXXXX),

where the symbols R¹, R³ and the indices m and n are as defined aboveand M is Rh or Ir XX corresponds to the point of linkage in the polymer,YY is identical or different on each occurrence and is in each case O, Sor Se.
 7. The organic semiconductor according to claim 2, wherein thefollowing applies to the symbols of the formulae (1) to (5): X standsfor O, S or N—R⁴; Y stands for P or As; Z stands for S or Se; where atleast one of the substituents R¹ to R³ on each structural unit of theformula (1) to (5) represents an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which may be substituted by one or moresubstituents R⁴ or unsubstituted.
 8. The organic semiconductor accordingto claim 7, wherein applies to the symbols of the formulae (1) to (5): Xstands for O or N—R⁴; Y stands for P; Z stands for S; where allsubstituents R¹ to R³ on each structural unit of the formula (1) to (5)represent an aromatic or heteroaromatic ring system having 1 to 40 Catoms, which may be substituted by one or more substituents R⁴ orunsubstituted.
 9. The organic semiconductor according to claim 2,wherein the total proportion of structural units of the formula (1) to(5) is 10-50 mol %.
 10. The organic semiconductor according to claim 1,wherein at least one of the radicals R¹ to R³ contains a9,9′-spirobifluorene.
 11. The organic semiconductor according to claim1, wherein the polymers are selected from the classes of the aromaticpolyketones, aromatic polyphosphine oxides or aromatic polysulfones,each of which may also be substituted for better solubility, thepolycarboxylic acid derivatives, main-chain polyesters, side-chainpolyesters, poly(glycolic acids), poly(lactic acids),poly(ε-caprolactones), polyacrylates, poly(hydroxybenzoic acids),poly(alkylene terephthalates), polycarboxylic anhydrides, polyamides,poly(ε-caprolactams), polypeptides, polyaramids, polybenzamides,polyimides, poly(amide-imides), poly(ester-imides), poly(ether-imides),polycarbonates, poly (ester-co-carbonates), poly(isocyanurates),polyurethanes, polyester-polyurethanes, poly(terephthalates),poly(acrylates), poly(phenyl acrylates), poly(cyanoacrylates),poly(vinyl esters), poly(vinyl acetates), side-chain polyphosphineoxides, polyether ketones (PEK), polyether sulfones, poly-sulfonamides,polysulfonimides, poly(vinyl ketones), aromatic polyvinyl ketones,substituted or unsubstituted poly(vinylbenzophenones),polystyrene-analogous ketones, polycarbazenes, polynitriles,polyisonitriles, polystyrene, PVK (polyvinylcarbazole) or derivativesthereof.
 12. The organic semiconductor according to claim 1, wherein thetriplet emitters contain atoms from the Periodic Table of the Elementshaving an atomic number of greater than
 36. 13. The organicsemiconductor according to claim 12, wherein the triplet emitterscontain d or f transition metals.
 14. The organic semiconductoraccording to claim 13, wherein the triplet emitters contain metals fromgroup 8 to
 10. 15. The organic semiconductor according to claim 1,wherein further molecules, which may be of low molecular weight,oligomeric, dendritic or polymeric, are admixed with the organicsemiconductors.
 16. The organic semiconductor according to claim 15,wherein compounds containing structural units L=X or structural units ofthe formula (1) to (5) may additionally be admixed with the mixture

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹, R², R³ is oneach occurrence, identically or differently, H, F, CN, a straight-chain,branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 Catoms, which is optionally substituted by R⁵ or may also beunsubstituted, where one or more non-adjacent CH₂ groups is optionallyreplaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se,C═NR⁶, —O—, or —S—, and where one or more H atoms may be replaced by F,Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which is optionally substituted by one or moreradicals R⁵, where two or more substituents R¹, R² and/or R³ may alsowith one another form a mono- or polycyclic, aliphatic or aromatic ringsystem; all substituents R¹ to R³ on one structural unit here must notbe H or F; the groups R¹ to R³ may furthermore optionally have bonds tothe polymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms may bereplaced by fluorine, an aryl, heteroaryl or aryloxy group having 1 to40 C atoms, which may also be substituted by one or more radicals R⁶, orOH or N(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴or CN, B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically ordifferently, H or an aliphatic or aromatic hydrocarbon radical having 1to 20 C atoms.
 17. An electronic component which comprises one or moreactive layers, where at least one of these active layers comprises oneor more organic semiconductors according to claim
 1. 18. The electroniccomponent according to claim 17, wherein the component is an organiclight-emitting diode, an organic solar cell or an organic laser diode.19. A mixture (BLEND1), comprising (A) 5-99.9% by weight of at least onenon-conjugated polymer (POLY1) which comprises 1-100 mol % of one ormore recurring units (MONO1) containing at least one structural unit L=Xor at least one structural unit of the formula (1) to (5), wherein L ison each occurrence, identically or differently, (R¹)(R²)C, (R¹)P,(R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P, (R¹)(R²)(R³)As, (R¹)(R²)(R³)Sb,(R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se, (R¹)(R²)Te, (R¹)(R²)S(═O),(R¹)(R²)Se(═O) or (R¹)(R²)Te(═O); X is on each occurrence, identicallyor differently, O, S, Se or N—R⁴, with the proviso that X is not S or Seif L stands for S, Se or Te; R¹, R², R³ is on each occurrence,identically or differently, H, F, CN, a straight-chain, branched orcyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, whichis optionally substituted by R⁵ or may also be unsubstituted, where oneor more non-adjacent CH₂ groups may be replaced by —R⁶C═CR⁶—, —C≡C—,Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶, —O—, or —S— and whereone or more H atoms are optionally replaced by F, Cl, Br, I, CN or NO₂,or an aromatic or heteroaromatic ring system having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁵, where two ormore substituents R¹, R² and/or R³ may also with one another form amono- or polycyclic, aliphatic or aromatic ring system; all substituentsR¹ to R³ on one structural unit here must not be H or F; the groups R¹to R³ may furthermore optionally have bonds to the polymer; R⁴ is oneach occurrence, identically or differently, a straight-chain, branchedor cyclic alkyl or alkoxy chain having 1 to 22 C atoms, in which, inaddition, one or more non-adjacent C atoms may be replaced by —R⁶C═CR⁶,—C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—, —CO—O—, —O—CO—O—,where, in addition, one or more H atoms replaced by fluorine, an aryl,heteroaryl or aryloxy group having 1 to 40 C atoms, which is optionallysubstituted by one or more radicals R⁶, or OH or N(R⁵)₂; R⁵ is on eachoccurrence, identically or differently, R⁴ or CN, B(R⁶)₂ or Si(R⁶)₃, R⁶is on each occurrence, identically or differently, H or an aliphatic oraromatic hydrocarbon radical having 1 to 20 C atoms; and wherein theformulae (1) to (5) are as follows:

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹ to R⁶ have thesame meaning as described above, and (B) 0.1-95% by weight of one ormore triplet emitters (TRIP1).
 20. An organic semiconductor whichcomprises the mixture according to claim 19, wherein the recurring units(MONO1) which contain structural elements L=X or structural elements ofthe formula (1) to (5) are selected from the formulae (6) to (148),which may be substituted or unsubstituted

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹, R², R³ is oneach occurrence, identically or differently, H, F, CN, a straight-chain,branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 Catoms, which may be substituted by R⁵ or may also be unsubstituted,where one or more non-adjacent CH₂ groups may be replaced by —R⁶C═CR⁶—,—C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶, —O—, or —S—,and where one or more H atoms is optionally replaced by F, Cl, Br, I, CNor NO₂, or an aromatic or heteroaromatic ring system having 1 to 40 Catoms, which is optionally substituted by one or more radicals R⁵, wheretwo or more substituents R¹, R² and/or R³ may also with one another forma mono- or polycyclic, aliphatic or aromatic ring system; allsubstituents R¹ to R³ on one structural unit here must not be H or F;the groups R¹ to R³ may furthermore optionally have bonds to thepolymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms is optionallyreplaced by fluorine, an aryl, heteroaryl or aryloxy group having 1 to40 C atoms, which may also be substituted by one or more radicals R⁶, orOH or N(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴or CN, B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically ordifferently, H or an aliphatic or aromatic hydrocarbon radical having 1to 20 C atoms,


21. A mixture (BLEND2), comprising (A) 0.5-99% by weight of at least onenon-conjugated polymer (POLY2) which comprises 0.5-99.5 mol % of one ormore triplet emitters (TRIP2) covalently bonded, and (B) 1-99.5% byweight of at least one compound (COMP1) which contains at least onestructural unit L=X or at least one structural unit of the formula (1)to (5) wherein L is on each occurrence, identically or differently,(R¹)(R²)C, (R¹)P, (R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P, (R¹)(R²)(R³)As,(R¹)(R²)(R³)Sb, (R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se, (R¹)(R²)Te,(R¹)(R²)S(═O), (R¹)(R²)Se(═O) or (R¹)(R²)Te(═O); X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X is not S or Se if L stands for S, Se or Te; R¹, R², R³ ison each occurrence, identically or differently, H, F, CN, astraight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 C atoms, which is optionally substituted by R⁵ or mayalso be unsubstituted, where one or more non-adjacent CH₂ groups may bereplaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se,C═NR⁶, —O—, or —S— and where one or more H atoms are optionally replacedby F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which is optionally substituted by one or moreradicals R⁵, where two or more substituents R¹, R² and/or R³ may alsowith one another form a mono- or polycyclic, aliphatic or aromatic ringsystem; all substituents R¹ to R³ on one structural unit here must notbe H or F; the groups R¹ to R³ may furthermore optionally have bonds tothe polymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms replaced byfluorine, an aryl, heteroaryl or aryloxy group having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁶, or OH orN(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴ or CN,B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically or differently,H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 Catoms; and wherein the formulae (1) to (5) are as follows:

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹ to R⁶ aredefined above, and is capable of forming glass-like layers at roomtemperature.
 22. A mixture (BLEND3), comprising (A) 0.5-98.9% by weightof at least one non-conjugated polymer (POLY3), and (B) 1-99% by weightof at least one compound (COMP1) which contains at least one structuralunit L=X or at least one structural unit of the formula (1) to (5) andis capable of forming glass-like layers at room temperature, wherein Lis on each occurrence, identically or differently, (R¹)(R²)C, (R¹)P,(R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P, (R¹)(R²)(R³)As, (R¹)(R²)(R³)Sb,(R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se, (R¹)(R²)Te, (R¹)(R²)S(═O),(R¹)(R²)Se(═O) or (R¹)(R²)Te(═O); X is on each occurrence, identicallyor differently, O, S, Se or N—R⁴, with the proviso that X is not S or Seif L stands for S, Se or Te; R¹, R², R³ is on each occurrence,identically or differently, H, F, CN, a straight-chain, branched orcyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms, whichis optionally substituted by R⁵ or may also be unsubstituted, where oneor more non-adjacent CH₂ groups may be replaced by —R⁶C═CR⁶—, —C≡C—,Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶, —O—, or —S— and whereone or more H atoms are optionally replaced by F, Cl, Br, I, CN or NO₂,or an aromatic or heteroaromatic ring system having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁵, where two ormore substituents R¹, R² and/or R³ may also with one another form amono- or polycyclic, aliphatic or aromatic ring system; all substituentsR¹ to R³ on one structural unit here must not be H or F; the groups R¹to R³ may furthermore optionally have bonds to the polymer; R⁴ is oneach occurrence, identically or differently, a straight-chain, branchedor cyclic alkyl or alkoxy chain having 1 to 22 C atoms, in which, inaddition, one or more non-adjacent C atoms may be replaced by —R⁶C═CR⁶,—C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—, —CO—O—, —O—CO—O—,where, in addition, one or more H atoms replaced by fluorine, an aryl,heteroaryl or aryloxy group having 1 to 40 C atoms, which is optionallysubstituted by one or more radicals R⁶, or OH or N(R⁵)₂; R⁵ is on eachoccurrence, identically or differently, R⁴ or CN, B(R⁶)₂ or Si(R⁶)₃, R⁶is on each occurrence, identically or differently, H or an aliphatic oraromatic hydrocarbon radical having 1 to 20 C atoms; and wherein theformulae (1) to (5) are as follows:

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹ to R⁶ aredefined above, and (C) 0.1-95% by weight of one or more triplet emitters(TRIP1).
 23. An organic semiconductor which comprises the mixtureaccording to claim 22, wherein the compound (COMP 1) which containsstructural elements L=X or structural elements of the formulae (1) to(5) is selected from the formulae (6) to (148), which is optionallysubstituted or unsubstituted and wherein

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹, R², R³ is oneach occurrence, identically or differently, H, F, CN, a straight-chain,branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 Catoms, which may be substituted by R⁵ or may also be unsubstituted,where one or more non-adjacent CH₂ groups may be replaced by —R⁶C═CR⁶—,—C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶, —O—, or —S—,and where one or more H atoms is optionally replaced by F, Cl, Br, I, CNor NO₂, or an aromatic or heteroaromatic ring system having 1 to 40 Catoms, which is optionally substituted by one or more radicals R⁵, wheretwo or more substituents R¹, R² and/or R³ may also with one another forma mono- or polycyclic, aliphatic or aromatic ring system; allsubstituents R¹ to R³ on one structural unit here must not be H or F;the groups R¹ to R³ may furthermore optionally have bonds to thepolymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms isoptionally replaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂,—NR⁶—, —O—, —S—, —CO—O—, —O—CO—O—, where, in addition, one or more Hatoms is optionally replaced by fluorine, an aryl, heteroaryl or aryloxygroup having 1 to 40 C atoms, which may also be substituted by one ormore radicals R⁶, or OH or N(R⁵)₂; R⁵ is on each occurrence, identicallyor differently, R⁴ or CN, B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence,identically or differently, H or an aliphatic or aromatic hydrocarbonradical having 1 to 20 C atoms,


24. A mixture (BLEND4), comprising (A) 0.5-99% by weight of at least onenon-conjugated polymer (POLY3); and (B) 1-99.5% by weight of a compound(TRIP3) which contains at least one structural unit L=X or at least onestructural unit of the formula (1) to (5) covalently bonded to one ormore triplet emitters, wherein L is on each occurrence, identically ordifferently, (R¹)(R²)C, (R¹)P, (R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P,(R¹)(R²)(R³)As, (R¹)(R²)(R³)Sb, (R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se,(R¹)(R²)Te, (R¹)(R²)S(═O), (R¹)(R²)Se(═O) or (R¹)(R²)Te(═O); X is oneach occurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X is not S or Se if L stands for S, Se or Te; R¹, R², R³ ison each occurrence, identically or differently, H, F, CN, astraight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 C atoms, which is optionally substituted by R⁵ or mayalso be unsubstituted, where one or more non-adjacent CH₂ groups may bereplaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se,C═NR⁶, —O—, or —S— and where one or more H atoms are optionally replacedby F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which is optionally substituted by one or moreradicals R⁵, where two or more substituents R¹, R² and/or R³ may alsowith one another form a mono- or polycyclic, aliphatic or aromatic ringsystem; all substituents R¹ to R³ on one structural unit here must notbe H or F; the groups R¹ to R³ may furthermore optionally have bonds tothe polymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms replaced byfluorine, an aryl, heteroaryl or aryloxy group having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁶, or OH orN(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴ or CN,B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically or differently,H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 Catoms; and wherein the formulae (1) to (5) are as follows:

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹ to R⁶ aredefined above, where the bonding between the triplet emitter and thestructural unit L=X can take place in any desired positions of the twounits, with the restriction that at least one group X in (TRIP3) must bein free form and not coordinated to a metal atom.
 25. An organicsemiconductor which comprises the mixture according to claim 24, whereinthe compound (TRIP3) contains structural elements which are selectedfrom the formulae (6) to (148), which may be substituted orunsubstituted


26. A polymer POLY4 comprising (A) 1 -99.9 mol % of one or morerecurring units MONO1 containing at least one structural unit L=Xwherein L is on each occurrence, identically or differently, (R¹)(R²)C,(R¹)P, (R¹)As, (R¹)Sb, (R¹)Bi, (R¹)(R²)(R³)P, (R¹)(R²)(R³)As,(R¹)(R²)(R³)Sb, (R¹)(R²)(R³)Bi, (R¹)(R²)S, (R¹)(R²)Se, (R¹)(R²)Te,(R¹)(R²)S(═O), (R¹)(R²)Se(═O) or (R¹)(R²)Te(═O); X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X is not S or Se if L stands for S, Se or Te; R¹, R², R³ ison each occurrence, identically or differently, H, F, CN, astraight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy grouphaving 1 to 40 C atoms, which is optionally substituted by R⁵ or mayalso be unsubstituted, where one or more non-adjacent CH₂ groups may bereplaced by —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se,C═NR⁶, —O—, or —S— and where one or more H atoms are optionally replacedby F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which is optionally substituted by one or moreradicals R⁵, where two or more substituents R¹, R² and/or R³ may alsowith one another form a mono- or polycyclic, aliphatic or aromatic ringsystem; all substituents R¹ to R³ on one structural unit here must notbe H or F; the groups R¹ to R³ may furthermore optionally have bonds tothe polymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms replaced byfluorine, an aryl, heteroaryl or aryloxy group having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁶, or OH orN(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴ or CN,B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically or differently,H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 Catoms; (B) 0.1-95 mol % of one or more triplet emitters TRIP2.
 27. Apolymer containing one or more structural units of the formula (1) to(5) and 9,9′-spirobifluorene units

where the symbols used have the following meaning: X is on eachoccurrence, identically or differently, O, S, Se or N—R⁴, with theproviso that X cannot be S or Se for formulae (4) and (5); Y is on eachoccurrence, identically or differently, P, As, Sb or Bi; Z is on eachoccurrence, identically or differently, S, Se or Te; R¹, R², R³ is oneach occurrence, identically or differently, H, F, CN, a straight-chain,branched or cyclic alkyl, alkoxy or thioalkoxy group having 1 to 40 Catoms, which is optionally substituted by R⁵ or may also beunsubstituted, where one or more non-adjacent CH₂ groups may be replacedby —R⁶C═CR⁶—, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶,—O—, or —S— and where one or more H atoms are optionally replaced by F,Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 1 to 40 C atoms, which is optionally substituted by one or moreradicals R⁵, where two or more substituents R¹, R² and/or R³ may alsowith one another form a mono- or polycyclic, aliphatic or aromatic ringsystem; all substituents R¹ to R³ on one structural unit here must notbe H or F; the groups R¹ to R³ may furthermore optionally have bonds tothe polymer; R⁴ is on each occurrence, identically or differently, astraight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22C atoms, in which, in addition, one or more non-adjacent C atoms may bereplaced by —R⁶C═CR⁶, —C≡C—, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, —NR⁶—, —O—, —S—,—CO—O—, —O—CO—O—, where, in addition, one or more H atoms replaced byfluorine, an aryl, heteroaryl or aryloxy group having 1 to 40 C atoms,which is optionally substituted by one or more radicals R⁶, or OH orN(R⁵)₂; R⁵ is on each occurrence, identically or differently, R⁴ or CN,B(R⁶)₂ or Si(R⁶)₃, R⁶ is on each occurrence, identically or differently,H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 Catoms.